S-(3-alkylmercapto 2-halo propyl) and s-(3-alkylmercapto 2-halo propenyl) esters of pentavalent phosphorus acids



, 3,l53,6fii Patented Oct. 20, 1964 3153 664 ss-ALrrrrMsncAmio i-r-rALo PROPYL) AND S-(3-ALKYLMEIRCAPTO 2-HALO rnorsNrL EsTEns or PENTAVALENT rnosrnonns In accordance with this invention it has now been found that compounds of the above inventive composition, which are also highly effective as insecticides, can be obtained by addition of optionally substituted alkylor and- AQES Hans-Gerri senate, WllPpertal-Elberfeid, and Gerhard 5 Sufism 9 hand itl y t of Schmder, wuppertabcmnwberg Germany, assignms phosphoric (-phosphonic, -phosp mic) ac1d esters of the t0 Farbenfabriken Bayer Aktiengesellschatt, Leverformula kusen, Germany, a corporation of Germany Rt ms) R3 R4 N0 Drawing. Filed Aug. 22, 1%2, Ser. No. 218,506

Claims priority, application Germany Sept. 6, 1961 10 P CHi-O=OH 11 Claims. (Cl. 260-461) R2 The present invention relates to and has as its objects new and useful insecticidal (di)thiophosphoric acid esters 111 Whlch the y have the Same slgnlficance as given and processes for their production. Generally the new abOVecompounds of this invention may be represented by the 15 The reactlon in accordance W (the Process can be following formula plained by means of the following reaction sequence:

R1\ R3 R4 R O s R PsoH,-o-oH-s m R3 4 I P-sorno=o11 HalS-R5 R: Hal in which R and R denote aliphatic or aromatic residues 0(3) which are linked to the phosphorus atom either directly \iL or via oxygen, R and R represent hydrogen or another 2 5 CC bond, whilst R signifies an alkyl radical and Hal a R! halogen atom, preferably chlorine.

0,0-dialkyl-S-propargyl-thioor -dithiophosphoric acid where again the residues R to R possess the significance esters of the general formula specified above.

The process according to the invention is preferably di carried out at room temperature or at a lower tempera- P-S-CHz-CECH ture, and in the presence of inert organic solvents. R0 Among the latter, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, and wherein R represents, preferably lower, alkyl r id carbon tetrachloride have proved particularly suitable. have already been described in German patent specifica- It as a s en f und that t C mpounds obtainable tion 1,063,148. according to the process possess a considerably increased In accordance with the above mentioned German p t insecticidal activity compared with the alkenylor alkyent specification these compounds are characterized by nyl-thioor drthiophosphoric (-phosphonic, -phosphinic) good insecticidal activity towards Colorado beetles, flies, acid esters to be employed as starting materials; these ungreenflies, spider mites, and mosquito larvae, and in part expected, technically valuable properties of the products they possess systemic properties. of the process are evident from thefollowing comparison:

Biological activity Product Cone. of Destruc- Appl. againstactive tion of agent pests (percent) (percent) (CgH O)2] r SCH2Cl-I=C Gr enflies 0. 1 0 Spider mites 0. 1 0 i Fly maggots 0. l (C2H5O)zP-S-CH CECH Greenfiies 0.1 so 7 Spider mites 0. 1 H $1 Fly maggots 0. 1 CzH5O)zPSCHzCHCHz-S0211 Greenfiies 0 l 100 Spider mites 0. 01 100 Fly maggots- 0.001 50 (iC3H70)zP-SCHz-CH=CH2 IBB lE 0.1 0 S Spider mites, 0. l 40 (iC H7O)zli-SCHCECH Greenflies 0.1 0 Spider mites 0. 1 0 n i (iCaH1O)ZPSCH CH-OH SC2115 l. Greenfiies 0.01 100 Spider mites 0. 1 100 Ki P-SOHg-CH=CH2 Greenflies 0. 1 95 Spider mites 0. l 98 CzHaO O Greenflies I 0.1 100 Spider mites. 0. 1 100 Biological activity Product Cone. of Destruc:

Appl. agalnstactive tion of agent pests (percent) (percent) Kt I PSOH;;-OHCHZS C2H5 Greenflies 0. 01 100 Spider mites O. 01 100 01121 (ovicidal activity.)

i CzH )zPSCHzOH=CH2. Greenfiins 0 1 40 Spider mites 0. 1 50 ll (C2H5)2PSCE2CECH Grcenflips 0. 1 50 Spider mites 0. 1 100 II I (O H5)iP-SCHiC=CH-S C211 Greenflins 0. 1 100 Spider mites 0. 01 100 By virtue of this excellent insecticidal activity, the thi0- phosphoric (-phosphonic, -phosphinic) or dithiophosphoric (-phosphonic, -phosphinic) acid esters according to the invention are applicable as pest control agents, particularly for plant protection.

The application of the products of the process for the stated purpose is carried out by the normal method for insecticides based on phosphoric acid esters, i.e. preferably in combination with solid or liquid extenders or diluents. Examples of solid extenders are talc, chalk, bentonite, alumina, kaolin, and the like, whilst Water is principally employed for the preparation of liquid formulations. Since the compounds according to the invention are very largely insoluble in water, however, the application of a solubilizing assistant, e.g. dimethylformamide or acetone, and also of a commercial emulsifying agent, is recommended in such a case.

The following examples are given for the purpose of illustrating the present invention.

Example 1 CgHBO S aHsO 68 grams (0.3 mol) of 0,0-dietl1ylthionothiolphosphoric acid-S-propenyl-(2)-ester are dissolved in 100 cc. of carbon tetrachloride. 29 grams of ethylsulfenic acid chloride, dissolved in 100 cc. of carbon tetrachloride, are then added dropwise to this solution at 0 C., the mixture is thereafter stirred for another 30 minutes, washed with water, the organic phase dried, and the solvent distilled off. The yield amounts to 82 grams, corresponding to 85% of the theoretical. The 0,0-diethylthiono-thiolphosphoric acid S (2-chloro-3-ethyl-mercaptopropyl)- ester is obtained in the form of an almost colorless oil.

Analysis.Calculated for a molecular Weight of 322: P, 9.63%; S, 29.8%; C1, 11.01%. Found: P, 9.53%; S, 29.68%; Cl, 10.80%.

Example 2 0.3 mol of ethylsulfenic acid chloride, dissolved in 200 cc. of carbon tetrachloride, are added dropwise at C. to a solution of 63 grams (0.3 mol) of 0,0-diethylthiophosphoric acid-S-propenyl-(2)-ester in 200 cc. of carbon tetrachloride, and the mixture is thereafter stirred at C. for another hour. The resultant colorless solution is then washed with water, and dried. When the solvent has been distilled oi, the 0,0-diethylthiolphosphoric acid-S-(2-chloro-3-ethylmercaptopropyl)-ester remains as an oil with a pale yellow color. The yield amounts to 83 grams, corresponding to of the theoretical.

Analysis.Calcaluted for a molecular weight of 306.5: P, 10.12%; S, 20.9%; C1, 11.6%. Found: P, 9.98%;

S, 21.05%; Cl, 11.38%.

Example 3 PSCHQ CHOHB-SCZHQ iOaH1O 38 grams (0.15 mol) of 0,0-diisopropylthionothiolphosphoric acid-S-propenyl-(Z)-ester are dissolved in 200 cc. of carbon tetrachloride; this solution is treated dropwlse at O to 5 C. with 0.15 mol of ethylsulfenic acid chloride dissolved in 75 cc. of carbon tetrachloride, the mixture is thereafter stirred at 20 C. for another hour, and then washed with water. After the organic phase has been dried over sodium sulfate, the solvent is removed in vacuum. There remain 45 grams (86% of the theoretical) of 0,0-dissopropylthionothiolphosphoric acid-S-(2-chloro-3-ethylmercaptopropyl) -ester in the form of an almost colorless oil.

Analysis.Calculated for a molecular weight of 350.5: P, 8.86%; S, 27.4%; Cl, 10.12%. Found: P, 9.35%; s, 27.02%; 01, 9.10%.

Example 4 31.5 grams (0.15 mol) of ethylthionothiolphosphonic acid-O-ethyl-S-propenyl-(:2)-ester are dissolved in 200 cc. of carbon tetrachloride. 0.15 mol of ethylsulfenic acid chloride dissolved in 75 cc. of carbon tetrachloride, are added to this solution at 0 to 5 C., the reaction mixture is stirred at 20 C. for another hour, then washed with water, the organic layer is dried, and the solvent is removed in vacuum. There are obtained 43 grams (94% of the theoretical) of ethylthionothiolphosphonic acid-O- ethyl-S-(2-chloro-3-ethylmercaptopropyl)-ester as an almost colorless oil.

Analysis.-Ca1culated for a molecular weight of 306.5: P, 10.12%; S, 31.4%; C1, 11.6%. Found: P, 11.11%; S, 31.5%; C1, 10.57%.

By the same way but using ethylsulfenic acid bromide instead of the corresponding chloride there may be obtained the following compound Example 5 CzHaO 0.15 mol of methylsulfenic acid chloride, dissolved in 75 cc. of carbon tetrachloride, are added dropwise at to C. to a solution of 25.8 grams (0.1 mol) of phenylthionothiolphosphonic acid-O-ethyl-S-propenyl-(2)-ester, and the reaction mixture is worked up as described in the preceding examples. There are obtained 32 grams (94% of the theoretical) of phenylthionothiol-phosphonic acid- O-ethyl-S-( 2-chloro-3-methyl-mercaptopropyl -ester.

Analysis.Calculated for a molecular weight of 340.5: P, 9.13%; Cl, 10.43%. Found: P, 9.99%; Cl, 9.60%.

Example 6 A solution of 19.4 grams (0.1 mol) of diethylthionothiolphosphinic acid-S-propenyl(2)-ester in 150 cc. of carbon tetrachloride is treated dropwise at 0 to 5 C. with 8.25 grams (0.1 mol) of methyl-sulfenic acid chloride dissolved in 50 cc. of carbon tetrachloride. The reaction mixture is worked up as described in Examples 1 to 4, and there are obtained 24 grams (87% of the theoretical) of diethylthionothiolphosphinic acid-S-(2-chloro-3-methylmercapto-propyl) ester in the form of a pale yellow oil.

Analysis-Calculated for a molecular weight of 276.5: P, 11.25%; S, 34.80%; Cl, 12.88%. Found: P, 11.18%; S, 34.46%; Cl, 132.89%.

Example 7 67 grams (0.3 mol) of 0,0-diethylthionothiolphosphoric acid-S-propynyl-(2)-ester are dissolved in 100 cc. of carbon tetrachloride. 29 grams (0.3 mol) of ethylsulfenic acid chloride dissolved in 100 cc. of carbon tetrachloride are added dropwise to this solution, the mixture is thereafter stirred at room temperature for another hour, then washed with water, the organic phase dried, and the solvent distilled off in vacuum at a bath temperature of 30 to 40 C. The yield of 0,0-diethylthionothiolphosphoric acid-S-(2-chloro-3-ethyl-mercapt0propenyl)-ester amounts to 88 grams (92% of theoretical).

Analysis.Calculated for molecular weight of 320: P, 9.7%; S, 30.0%; C1, 11.1%. Found: P, 9.73%; S, 30.05%; Cl, 10.78%.

Example 8 C 2H5 O O 0.3 mol of ethylsulfenic acid chloride dissolved in 200 cc. of carbon tetrachloride are added dropwise at 10 C. to a solution of 62.5 grams (0.3 mol) of 0,0-diethylphosphoric acid-S-pnopynyl-(Z)-ester in 200 cc. of carbon tetrachloride, the reaction mixture is subsequently stirred at C. for another hour, then Washed with water, and after the organic phase has been dried over sodium sulfate, the solvent is removed in vacuum. There are obtained 60 grams (66% of the theoretical) of 0,0-diethylthiolphosphoric acid S (2 chloro-S-ethylmercaptoprm penyl)-ester in the form of a yellow oil.

Analysis.--Calculated for a molecular weight of 305.5: P, 10.15%; S, 21.0%; C1, 11.63%. Found: P, 10.33%; S, 20.97%; Cl, 10.92%.

Example 9 Kl r P-S-OH3-C=OHSCZH5 (321150 29 grams (0.15 mol) of methyl-thionothiolphosphonic acid-O-ethyl-S-propynyl-(2) ester are dissolved in 200 cc. of carbon tetrachloride, 0.15 mol of ethylsulfenic acid chloride dissolved in 75 cc. of carbon tetrachloride are added dropwise at 0 to 5 C. to this solution, and the reaction mixture is worked up as described in the preceding example. The yield amounts to 36 grams (83% of the theoretical).

Analysis.--Calculated for a molecular weight of 290.5: P, 10.7%; C1, 12.25%. Found: P, 10.6%; C1, 11.80%.

Example 10 0am s 01 S-CHz-C=OHSO:H6

0 A solution of 0.15 mol of ethylsulfenic acid chloride in 75 cc. of carbon tetrachloride is added dropwise at 0 to 5 C. to a solution of 29 grams of diethylthionothiolphosphinic acid-S-propynyl-(Z) ester in 200 cc. of carbon tetrachloride, the reaction mixture is thereafter worked up as described in the preceding examples, and there are obtained 36 grams (83 of the theoretical) of diethylthionothiolphosphinic acid S (2 chloro-3-ethyhnercaptopropenyD-ester in the form of a yellow oil.

Analysis.Calculated for molecular Weight of 288.5: P, 11.08%; S, 34.3%. Found: P, 10.71%; S, 34.89%.

We claim: 1. A compound of the formula wherein R is lower alkyl having up to 4 carbon atoms, R is lower alkoxy having up to 4 carbon atoms, R is lower alkyl having up to 4 carbon atoms, Hal stands for a member selected from the group consisting of bromo and chloro and X stands for a member selected from the group consisting of oxygen and sulfur.

2. A compound of the formula wherein R and R are each lower alkyl having up to 4 carbon atoms, R is lower alkyl having up to 4 carbon atoms, Hal stands for a member selected from the group consisting of bromo and chloro and X stands for a member selected from the gnoup consisting of oxygen and sulfur.

3. A compound of the formula \l] /PSCHn-C=CHSR5 R Hal wherein R and R stand for a member selected from the group consisting of lower alkyl having up to 4 carbon atoms and lower alkoxy having up to 4 carbon atoms, and phenyl, and R stands for lower alkyl having up to 4 carbon atoms, Hal stands for a member selected from the group consisting of chloro and bromo, and X stands for a member selected from the group consisting of oxygen and sulfur.

4. The compound [of the following formula 7 8 5. The compound of the following formula 8. The compound of the following formula CH3 S 01 \II Q 01 /PSOHg-C=OHSC1H5 i SCH ]HOH SOH 5 02H) 021150 7 9. A compound of claim 2 wherein R and R are each lower alkoxy having up to 4 carbon atoms. U 10. A compound of claim 2 wherein R is lower alkyl The compound of the followm formula having up to 4 carbon atoms and R is lower alkoXy 10 having up to 4 carbon atoms. f 11. A compound of claim 2 wherein R and R are P-S-CHz-C=OHSC2H5 each lower alkyl having up to 4- carbon atoms.

' 021150 References Cited in the file of this patent '7. The compound of the following formula 15 UNITED STATES PATENTS 2,952,700 Lorenz et a1 Sept. 13, 1960 o2H50\ ('31 2,976,309 Schrader Mar. 21, 1961 /PSCH;C=OHS-G2H5 FOREIGN PATENTS 021150 20 F15647 Germany Feb. 23, 1956 F16085 Germany Feb. 23, 1956 

1. A COMPOUND OF THE FORMULA
 2. A COMPOUND OF THE FORMULA
 3. A COMPOUND OF THE FORMULA 